CN1324078C - Composite polymer particle and method for preparing same - Google Patents

Composite polymer particle and method for preparing same Download PDF

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CN1324078C
CN1324078C CN 03158022 CN03158022A CN1324078C CN 1324078 C CN1324078 C CN 1324078C CN 03158022 CN03158022 CN 03158022 CN 03158022 A CN03158022 A CN 03158022A CN 1324078 C CN1324078 C CN 1324078C
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polymer particles
composite polymer
mass
cosmetic
metal oxide
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CN 03158022
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CN1488666A (en )
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辻诚
南部博美
井上真
菅原智
猪股幸雄
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花王株式会社
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/61Surface treated
    • A61K2800/62Coated
    • A61K2800/63More than one coating
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/65Characterized by the composition of the particulate/core
    • A61K2800/651The particulate/core comprising inorganic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2998Coated including synthetic resin or polymer

Abstract

提供即使在W/O乳化化妆品中,配合稳定性也优良、紫外线防御效果高、使用感也良好的复合聚合物粒子,其制造方法和含有该复合聚合物粒子的化妆品。 Providing even when W / O emulsified cosmetic with excellent stability, high ultraviolet protection effect, feeling of use was good composite polymer particles, and a method of manufacturing the cosmetics containing the composite polymer particles. 含有用硅氧烷和/或氟化合物被覆的、平均粒径1μm以下的金属氧化物,使相对全单体和交联剂的合计100质量份是25质量份以上、按照Fedors方法计算出的溶解度参数不到8.9的乙烯基单体和交联剂进行聚合而得到的复合聚合物粒子,进而是含有用硅氧烷和/或氟化合物被覆的、平均粒径1μm以下的金属氧化物的复合聚合物粒子,是在化妆品中,含有作为金属氧化物量相当于5质量%量的复合聚合物粒子、和1质量%的4-甲氧基肉桂酸(2-乙基己酯)的化妆品的SPF为7以上的复合聚合物粒子,其制造方法和含有该复合聚合物粒子的化妆品。 Containing a metal oxide with a silicone and / or fluorine compounds in the coating, the average particle diameter of 1μm or less, the relative whole monomer and a crosslinker is a total of 100 parts by mass 25 parts by mass or more, calculated according to the method of Fedors solubility composite polymer particle parameters less than 8.9 vinyl monomer and a crosslinking agent obtained by polymerizing, further containing a silicone compound with a polymerization and / or coated with the fluorine compound, the average particle diameter of 1μm or less of the metal oxide compound particles, in cosmetics, as a metal oxide containing an amount equivalent to 5 mass% of the amount of cosmetic composite polymer particles, and 1 mass% of 4-methoxy cinnamate (2-ethylhexyl) of an SPF 7 above composite polymer particles, and a method for producing a cosmetic containing the composite polymer particles. 另外,化妆品也可以含有(A)一次粒子的平均粒径为0.01~0.1μm,具有紫外线防御能力和可见光的透过性的微粒子金属氧化物以及(B)平均大小为0.1μm~1μm、平均厚度为0.01μm~0.2μm的薄片状氧化锌。 Furthermore, the cosmetic may contain (A) average primary particle size of 0.01 ~ 0.1μm, having fine through and ultraviolet protection property and metal oxide (B) The average size of 0.1μm ~ 1μm, the average thickness of the visible light is 0.01μm ~ 0.2μm of flaky zinc oxide.

Description

复合聚合物粒子及其制造方法 Method for producing composite polymer particles and

技术领域 FIELD

本发明是关于对W/O系化妆品的配合稳定性、使用感和紫外线防御能力优良的含有金属氧化物的复合聚合物粒子,其制造方法及含有该复合聚合物粒子的化妆品。 The present invention relates to the stability of the complex W / O-based cosmetics, UV protection ability and the feeling in use fine polymer particles containing a composite metal oxide, and a method for producing cosmetics containing the composite polymer particles.

背景技术 Background technique

在化妆品中,以保护皮肤不受紫外线伤害为目的,配合紫外线吸收剂。 In cosmetics to protect the skin from UV rays for the purpose ultraviolet absorber. 紫外线吸收剂可大致分为有机系和无机系,前者可举出肉桂酸衍生物、二苯甲酮衍生物、甲氨基苯甲酸衍生物、水杨酸衍生物等,后者可举出氧化锌、氧化钛、氧化铈、氧化铁等金属氧化物。 Ultraviolet absorbers can be roughly divided into organic and inorganic, the former may include cinnamic acid derivatives, benzophenone derivatives, carboxylic acid derivatives, salicylic acid derivatives, etc., which can include zinc oxide , titanium oxide, cerium oxide, iron oxide and other metal oxides. 在有机系紫外线吸收剂的情况下,吸收波长领域是低波长、化合物不稳定、浸透到皮肤中的效果不能持续是问题。 In the case where the organic ultraviolet absorbent, the absorption wavelength region is low wavelength, unstable compound, penetration into the skin effect does not continue to be a problem. 在无机系紫外线吸收剂的情况下,向配合系的分散性不好或使用感不太好是问题。 In the case where the inorganic ultraviolet absorber, based dispersibility with poor or very good feeling of use is a problem.

作为使向配合系的分散性和使用感并存的建议之一,已经知道金属氧化物的胶囊化。 So as to sense one of the dispersibility and the use of the coexistence system with the recommendations already known encapsulated metal oxide. 例如在JP-A9-208437中公开了在乳液化妆品中配合内包平均粒径0.003~0.1μm的金属氧化物的树脂粉体的化妆品。 For example, discloses cosmetic powder encapsulated with resin average particle diameter of the metal oxide is 0.003 ~ 0.1μm in the emulsion cosmetic in JP-A9-208437. 但是,在该方法中,为了使金属氧化物分散而使用离子性的分散剂,因此在树脂粉体的表面上部分存在金属氧化物的情况下,在W/O乳化化妆品中,金属氧化物的亲水部分发生凝集,在配合稳定性恶化的同时,也往往不能充分发挥紫外线防御效果。 However, in this method, in order to make the metal oxide dispersion using an ionic dispersant, there is a case where the metal oxide on the surface portion of the resin powder, the W / O emulsified cosmetic, metal oxides agglutination hydrophilic portion, while with deterioration of stability, often ultraviolet protection effect is not sufficiently exhibited.

另外,作为其他的尝试,通过使用组合数种粉体,正在研究兼具紫外线防御效果和使用感的两者的化妆品。 As another attempt, by using a combination of several kinds of powder, cosmetics are studying both both UV-protective effect and use feeling. 例如,在JP-A9-235217中公开了由配合内包氧化锌的粒径0.01~10μm的二氧化硅、粒径0.001~0.10μm的超微粒子氧化钛、及附着粒径0001~0.10μm的超微粒子氧化钛的板状滑石粉、云母和/或绢云母构成的无机粉体的化妆品。 For example, it discloses a bag with an inner diameter of zinc oxide in JP-A9-235217 0.01 to silica ultrafine particles, ultrafine particles of titanium oxide particle diameter of 0.001 ~ 0.10μm, and adhesion of 10μm diameter of 0001 ~ 0.10μm plate-like titanium oxide, talc, mica and / or sericite composed of inorganic powder cosmetic.

但是,内包这些金属氧化物的树脂粉体的单独,或者仅在其中组合超微粒子氧化钛,不能得到兼具所期待的充分UVA(紫外线A)防御效果和使用感及透明性的化妆品。 However, the resin encapsulated powder of these metal oxides alone, or in combination in which only ultrafine particles of titanium oxide, both can not be expected fully of UVA (ultraviolet A) shielding effect and transparency, and feeling of use of cosmetic.

发明内容 SUMMARY

本发明的课题在于提供,即使在W/O乳化化妆品中,配合稳定性优良、紫外线防御效果高、使用感良好的复合聚合物粒子,其制造方法及含有该复合聚合物粒子的化妆品。 Object of the present invention is to provide, even in the W / O emulsified cosmetic with excellent stability, high ultraviolet protection effects, excellent feeling of use composite polymer particles, and a method of manufacturing the cosmetics containing the composite polymer particles.

本发明的另外目的在于提供,高的紫外线防御效果、尤其具有高的长波长紫外线防御效果、透明性高、而且使用感良好的紫外线防御化妆品。 Further object of the present invention to provide a high ultraviolet protection effect, in particular a high long-wavelength ultraviolet shielding effect, high transparency, and good feeling in use ultraviolet protection cosmetic.

本发明人发现,通过将具有UVB(紫外线B)至UVAII的广泛领域的紫外线防御效果和可见光的透过性的微粒子金属氧化物、粒子形状是薄片状、从UVAII至近似可见光的UVAI的散射效果高的氧化锌、及内包微粒子金属氧化物的聚合物粒子的三种粉体组合使用,得到能够效率良好地提高紫外线防御效果、而且涂布时的透明性也高、进而使用感良好的紫外线防御化妆品。 The present inventors have found that, by having a wide range of fields ultraviolet protection effect UVB (ultraviolet B), and through to UVAII of the metal oxide fine particles, the particle shape is a sheet, to approximately from UVAII scattering effect of visible light of the visible light UVAI three kinds of zinc oxide powder combination of high, and a polymer encapsulated particles of metal oxide fine particles used, obtained can be efficiently improved ultraviolet protection effect, and the transparency is also high during coating, and further good feeling of use UV protection cosmetic.

本发明是含有用硅(silicone)/或氟化合物被覆的平均粒径1μm以下的金属氧化物、使相对全部单体和交联剂的合计100质量份是25质量份以上的利用Fedors方法计算的溶解度参数不到8.9的乙烯基单体与交联剂聚合而得到的复合聚合物粒子。 The present invention contains silicon (silicone) / a metal oxide or a fluorine compound-coated 1μm or less the average particle diameter, so that the total 100 parts by mass relative to all monomers and crosslinking agent is not less than 25 parts by mass of a calculation method using the Fedors the solubility parameter of less than 8.9 vinyl monomer with a crosslinking agent polymerized composite polymer particles obtained.

进而,是含有用硅/或氟化合物被覆的平均粒径1μm以下的金属氧化物的复合聚合物粒子,是在化妆品中,含有作为金属氧化物量相当于5质量%的上述复合聚合物粒子、及1质量%的4-甲氧基肉桂酸(2-乙基己酯)的化妆品的SPF为7以上的复合聚合物粒子。 Further, the average particle diameter contains silicon / or fluorine compound-coated composite polymer particles of 1μm or less of the metal oxide, in cosmetics, containing an amount of metal oxide corresponding to 5% by mass of the composite polymer particles, and 1 mass% of the cosmetic 4-methoxy cinnamate (2-ethylhexyl) SPF of 7 or more composite polymer particles.

另外,也提供上述复合聚合物粒子的制造方法。 Further, also provides a method for producing the composite polymer particles.

进而也提供含有上述复合聚合物粒子的化妆品,上述复合聚合物粒子的化妆品用途或者含有上述复合聚合物粒子和其他化妆品成分或化妆品载体的化妆品组合物。 And thus also to provide a cosmetic containing the composite polymer particles, the composite particles of the polymer or cosmetic use comprising the composite polymer particles and cosmetic compositions or other cosmetic ingredients of cosmetic carrier.

此外,本发明还提供含有以下的(A)、以下的(B)和上述化妆品的化妆品组合物。 Further, the present invention also provides a cosmetic composition comprising the following (A), the following (B) and said cosmetic.

(A)一次粒子的平均粒径是0.001~0.1μm、具有紫外线防御能力和可见光的透过性的微粒子金属氧化物。 (A) Average primary particle size was 0.001 ~ 0.1μm, and fine particles having ultraviolet protection visible metal oxide permeable.

(B)平均大小是0.1μm~1μm、平均厚度是0.01μm~0.2μm的薄片状氧化锌。 (B) is the average size of 0.1μm ~ 1μm, the average thickness of the flaky zinc oxide is 0.01μm ~ 0.2μm.

在上述化妆品组合物中,相对上述(A)成分和包含在复合聚合物粒子中的金属氧化物,最好以0.05~0.4的质量比含有成分(B)的薄片状氧化锌。 In the cosmetic composition, relative to the component (A) and a metal oxide contained in the composite polymer particles is preferably 0.05 to 0.4 mass a sheet comprising a thin zinc oxide ratio of component (B) is.

另外,本发明是提供,含有(A)一次粒子的平均粒径是0.001~0.1μm、具有紫外线防御能力和可见光的透过性的微粒子金属氧化物、(B)平均大小是0.1μm~1μm、平均厚度是0.01μm~0.2μm的薄片状氧化锌、以及内包(C)平均粒径是1~5μm、微粒子金属氧化物的聚合物粒子的紫外线防御化妆品。 Further, the present invention is provided, comprising (A) is the average primary particle size of 0.001 ~ 0.1μm, has the ultraviolet protection and the metal oxide fine particles permeable to visible light, (B) is the average size of 0.1μm ~ 1μm, the average thickness of the flaky zinc oxide 0.01μm ~ 0.2μm, and the inner bag (C) average particle size of 1 ~ 5μm, the polymer particles of the metal oxide fine ultraviolet protection cosmetic.

发明的具体实施方式 DETAILED EMBODIMENT OF THE INVENTION

[复合聚合物粒子]本发明的复合聚合物粒子,从紫外线防御能力高、使用感良好考虑,平均粒径较好是0.1~20μm,最好是1~20μm。 [Composite polymer particles] The composite polymer particles of the present invention, from a high UV protection ability, good feeling of use considerations, the average particle diameter is preferably 0.1 ~ 20μm, preferably 1 ~ 20μm. 在20μm以下,遮蔽面积变大,紫外线防御效果变高。 In 20μm or less, the shielding area becomes larger, an ultraviolet shielding effect becomes higher. 粒径如果过小,会产生“粗涩感”,因此最好是0.1μm以上。 If the particle size is too small, it will have a "Cuse flu", so it is best 0.1μm or more. 粒子的形状,没有特别的限制,但为了使用感良好,最好是球状。 The shape of the particles is not particularly limited, but in order to use a good feeling, preferably spherical.

再者,复合聚合物粒子的平均粒径是用激光(光)衍射/散射法(堀场制作所制LA-910)或者电阻法(库尔特计数器)测定的体积平均粒径。 Further, the average particle diameter of the composite polymer particles is a volume average particle diameter measured by a laser (light) diffraction / scattering method (manufactured by Horiba, Ltd. LA-910) or the electrical resistance method (a Coulter counter).

本发明的复合聚合物粒子,金属氧化物的含量较好是复合聚合物粒子全体的25~90质量%,最好是30~70质量%。 Composite polymer particles of the present invention, the content of the metal oxide is preferably 25 to 90 mass% of the total composite polymer particles, preferably 30 to 70 mass%. 在该范围内具有优良的紫外线防御能力。 Excellent in UV protection ability in this range.

本发明的复合聚合物粒子,在采用后述的试验例1的配合组成下的SPF的同一测定法测定的SPF最好是7以上。 Composite polymer particles of the present invention, measured with the same assay the SPF Test Example 1 described later employed in the composition is preferably at least 7 SPF.

即,本发明的复合聚合物粒子是含有用硅氧烷和/或氟化合物被覆的平均粒径1μm以下的金属氧化物的复合聚合物粒子,是在化妆品中,含有作为金属氧化物量相当于5质量%的上述复合聚合物粒子、及1质量%的4-甲氧基肉桂酸(2-乙基己酯)的化妆品的SPF为7以上的复合聚合物粒子。 That is, the composite particles of the present invention is a polymer having an average particle diameter of silicone and / or fluorine compound-coated composite polymer particles of 1μm or less of the metal oxide, in cosmetics, containing a metal oxide as an amount corresponding to 5 cosmetics mass% of the composite polymer particles, and 1 mass% of 4-methoxy cinnamate (2-ethylhexyl) SPF of 7 or more composite polymer particles.

含有作为金属氧化物量相当于5质量%的复合聚合物粒子、及1质量%的4-甲氧基肉桂酸(2-乙基己酯)的化妆品,为了在后述的测定法中的SPF成为7以上,金属氧化物需要分散在化妆品中。 As a metal oxide containing an amount equivalent to 5 mass% of the cosmetic composite polymer particles, and 1 mass% of 4-methoxy cinnamate (2-ethylhexyl), to be described later in SPF assay becomes 7 above, the metal oxide dispersed in a cosmetic need. 因此SPF也是表示金属氧化物在聚合物粒子中分散的分散指标。 SPF is thus represented by the metal oxide particles dispersed in a polymer dispersion index.

[金属氧化物]作为金属氧化物,可举出二氧化硅、氧化铁、氧化锆、氧化铝、氧化锌、氧化钛、氧化铈等,但从紫外线防御能力高考虑,最好是选自氧化锌、氧化钛和/或氧化铈组成的组中的1种以上。 [Metal oxide] as the metal oxide include silica, iron oxide, zirconium oxide, aluminum oxide, zinc oxide, titanium oxide, cerium oxide, but considered a high UV protection ability, preferably selected from oxide group of zinc, titanium oxide and / or cerium oxide consisting of one or more thereof.

金属氧化物,使用用硅氧烷和/或氟化合物被覆的金属氧化物。 A metal oxide, a metal oxide with a silicone and / or fluorine compounds coated. 用硅氧烷和/或氟化合物进行被覆,由于发生疏水化,和单体的分散性变得良好,与此同时,即使存在于复合聚合物粒子的表面上,金属氧化物表面也发生疏水化,因此在防止聚合物相互凝集的同时,紫外线防御能力变高。 Be coated with a silicone and / or fluorine compounds, due to the occurrence of hydrophobic, monomer and dispersibility becomes good, at the same time, even if present in the surface of the composite polymer particles on the metal oxide surface is also hydrophobized occur Therefore, while preventing mutual agglutination of polymer, high UV protection ability.

为了用硅氧烷和/或氟化合物进行被覆,最好进行金属氧化物的表面处理。 For coated with a silicone and / or fluorine compound is preferably subjected to a surface treatment of the metal oxide. 作为处理剂,可举出甲基氢化二烯聚硅氧烷,二甲基聚硅氧烷,如在特开平5-339518号公报中或特开平7-196946号公报中所记载具有羟基、卤原子、氨基羟基或者烷氧基等的反应性烷基聚硅氧烷(这些官能基可以在一末端、两末端、侧链中,也可以在硅原子中直接具有或者具有取代基,通过2价烃基结合),在特开平6-23262号公报中记载的含有氟基的氢化二烯聚硅氧烷等。 As a treatment agent include methylhydrogen polysiloxanes, dimethyl polysiloxane, as in JP-5-339518 or JP-A-7-196946 described as having a hydroxyl group, a halogen reactive atom, an amino group, a hydroxyl group or an alkoxy group such as polysiloxane (these functional groups may be at one end, both ends, side chain, may have a direct or a silicon atom in a substituent by bivalent hydrocarbyl binding) described in JP-a-6-23262 in hydrogenated diene containing fluorine and polysiloxane groups. 这些处理剂,如果需要,进行加热等,就能够与金属氧化物发生反应。 These treatment agents, if desired, heating or the like, can be reacted with a metal oxide. 另外,也能够使用市场上出售的、用硅氧烷和/或氟化合物被覆的金属氧化物。 Further, it is possible to use on the market, with a silicone and / or fluorine compound-coated metal oxide.

硅氧烷和/或氟化合物的被覆量,相对100质量份金属氧化物,较好是0.1~20质量份,最好是1~10质量份。 Silicone and / or coating amount of the fluorine compound, relative to 100 parts by mass of the metal oxide, preferably from 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass.

金属氧化物的平均粒径,从提高紫外线防御能力和复合聚合物粒子的透明性的观点出发,较好是1μm以下,更好是0.01~1μm,特别最好是0.1~1μm。 The average particle diameter of the metal oxide, from the viewpoint of improving the ultraviolet protection and transparency of the composite polymer particles of the starting, is preferably 1 m or less, more preferably 0.01 ~ 1μm, particularly preferably 0.1 ~ 1μm.

再有,金属氧化物的平均粒径是用动的光散射法(大电子制ELS-8000)测定的体积平均粒径。 Further, the average particle diameter of the metal oxide is the volume average particle diameter by light scattering method (manufactured by Great  electronic ELS-8000) measured dynamic.

[单体]作为本发明的复合聚合物粒子的原料使用的乙烯基单体,从提高用硅氧烷和/或氟化合物被覆的金属氧化物的分散性、尽可能地使金属氧化物的粒子内的不均匀化少的观点出发,较好是使用溶解度参数不到8.9的单体,最好是使用8.8以下的单体,从单体得到的难易度考虑,下限较好是6.0以上,最好是7.0以上。 [Monomer] The vinyl monomer raw material used in the composite polymer particles of the present invention, improving the dispersibility of the metal oxide with a silicone and / or fluorine compounds covered as much as possible of the particles of metal oxide less unevenness of view of the viewpoint of the solubility parameter of the monomer used is preferably less than 8.9, preferably 8.8 using the following monomers, considering the difficulty level obtained from a monomer, the lower limit is preferably at least 6.0, preferably 7.0 or more. 溶解度参数是将小数点的第2位的值四舍五入的值。 The solubility parameter is a value of the second bit value is rounded to the decimal point. 在溶解度参数高时,在单体中金属氧化物均匀地分散,但在聚合后的复合聚合物粒子中,金属氧化物聚集在表层附近,紫外线防御效果变低。 When high solubility parameter, the metal oxide is uniformly dispersed in the monomer, but the composite polymer particles after polymerization, gathered near the surface layer of metal oxide, an ultraviolet shielding effect becomes low.

再者,所谓本说明书中所说的溶解度参数,是按照Fedors的方法(RFFedors.Polyme.Eng.Sic.,14,147(1974)),以下述式(I)计算出的值δ(cal/cm3)1/2值(以下,也称做SP)。 Furthermore, the present specification, the term called solubility parameters, in accordance with the Fedors method (RFFedors.Polyme.Eng.Sic., 14,147 (1974)), the following formula (I) calculated value δ (cal / cm3) 1/2 value (hereinafter also referred to as SP).

SP=(ΣΔeiΣΔvi)1/2···(I)]]>作为溶解度参数不到8.9的乙烯基单体,可举出具有可以被氟化的碳原子数8以上(最好碳原子数8~40)的直链或者支链烷基的(甲基)丙烯酸烷基酯,最好是具有可以被氟化的碳原子数10~22的直链或者支链的烷基的(甲基)丙烯酸烷基酯,在分子链的一个末端具有自由基聚合性基的二甲基聚硅氧烷化合物。 SP = (& Sigma; & Delta; ei & Sigma; & Delta; vi) 1/2 & CenterDot; & CenterDot; & CenterDot; (I)]]> a solubility parameter vinyl monomer is less than 8.9, may include having may be fluorinated carbon atoms, (meth) acrylic acid alkyl ester having 8 or more (preferably 8 to 40 carbon atoms) linear or branched alkyl, preferably is a straight chain carbon atoms which may be fluorinated, or 10 to 22 dimethylpolysiloxane compound (meth) acrylate of a branched alkyl group, at one end of the molecular chain having a radical polymerizable group. 在此,所谓(甲基)丙烯酸酯,意味着丙烯酸酯或者甲基丙烯酸酯。 Here, the (meth) acrylate means acrylate or methacrylate. 作为具体例子,可举出(甲基)丙烯酸辛酯、(甲基)丙烯酸(2-乙基己酯)、(甲基)丙烯酸月桂酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕榈酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸异十八酯、(甲基)丙烯酸二十二酯、碳链6以上的(甲基)丙烯酸2-(全氟烷基)乙酯等。 Specific examples include (meth) acrylate, octyl (meth) acrylate, (2-ethylhexyl acrylate), (meth) acrylate, lauryl (meth) acrylate, myristyl acrylate, (meth) palmityl acrylate, (meth) acrylate, stearyl (meth) acrylate, stearyl (meth) acrylate, lauryl acrylate, carbon chain having 6 or more (meth) acrylate, 2- (perfluoroalkyl ) acrylate. 在一个末端具有自由基聚合性基的二甲基聚硅氧烷化合物,最好是以特开平11-181003号公报中记载的以通式(II)表示的化合物。 In a dimethylpolysiloxane compound having a radical polymerizable end group, the compound of JP-A No. 11-181003 described by the general formula (II) is preferably represented.

[式中,A:表示以CH2=C(R1)COO-、CH2=C(R1)CONR2-或者CH2=CH-C6H4-表示的基。 [In the formula, A: represents a group to CH2 = C (R1) COO-, CH2 = C (R1) CONR2- or CH2 = CH-C6H4- represented.

但,R1=H或者CH3、R2=H或者CYH2Y+1(Y=1~4的整数)B:表示以-(CH2O)m-CnH2n-(m=0或者1、n=1~10的整数)表示的基。 However, R1 = H or CH3, R2 = H or CYH2Y + (Y = an integer of 1 to 4.) 1 B: represented by - (CH2O) m-CnH2n- (m = 0 or 1, n = an integer of 1 to 10 ) group represented.

E:表示以CpH2p+1(p=1~4的整数)表示的基。 E: represents a group in CpH2p + 1 (p = an integer of 1 to 4) below.

a:表示3~1500的数。 a: represents a number from 3 to 1500. ]对于在一个末端具有自由基聚合性基的二甲基聚硅氧烷化合物的数均分子量(Mn)来说,没有特别的限制,但较好是500~100000,最好是1000~50000。 ] To the number of dimethylpolysiloxane compound having a radical polymerizable group end-average molecular weight (Mn) is not particularly limited, but is preferably from 500 to 100,000, preferably 1,000 to 50,000.

只要不损害本发明的效果,也可以使苯乙烯、甲基丙烯酸甲酯等溶解度参数是8.9以上的乙烯基单体进行共聚。 Unless the effect of the present invention, may be styrene, methyl methacrylate solubility parameter of 8.9 or more vinyl monomers copolymerized. 溶解度参数不到8.9的乙烯基单体,相对全部单体和交联剂的合计100质量份,较好是25质量份以上,最好是40质量份以上,较好是99.9质量份以下,更好是97质量份以下,特别最好是90质量份以下。 The solubility parameter of less than 8.9 vinyl monomers, relative to 100 parts by total mass of all monomers and crosslinking agent is preferably 25 parts by mass or more, preferably 40 parts by mass or more, preferably 99.9 parts by mass or less, and more preferably from 97 parts by mass, particularly preferably 90 parts by mass or less.

[交联剂]在本发明中,为了物理的和化学的使复合聚合物粒子的涂膜强固,使用交联剂。 [Crosslinking Agent] In the present invention, the composite polymer particles to the coating film strong physical and chemical crosslinking agent. 作为交联剂,可举出在分子中具有至少2个自由基聚合性基(反应性不饱和基)的交联性乙烯系化合物。 The crosslinking agent may include having at least two radical polymerizable groups in the molecule (reactive unsaturated group) of the crosslinkable vinyl compound.

作为具有至少2个自由基聚合性基的交联性乙烯系化合物的具体例子,可举出(1)具有二个以上的乙二醇二(甲基)丙烯酸酯、二甘醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸酯残基的多元醇的(甲基)丙烯酸酯化合物;(2)N-甲基烯丙基丙烯酰胺、N-乙烯基丙烯酰胺、N,N′-亚甲基双(甲基)丙烯酰胺、双丙烯酰胺乙酸等丙烯酰胺化合物;(3)二乙烯基苯、二乙烯基醚、二乙烯基亚乙基尿素等 As the cross having at least two radically polymerizable group Specific examples of the crosslinkable vinyl compound include (1) having two or more ethylene glycol di (meth) acrylate, diethylene glycol di (meth ) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic ester residue of a polyhydric alcohol (meth) acrylate compound; (2) N- methyl-allyl acrylamide, N- Yi Xiji acrylamide, N , N'- methylene-bis (meth) acrylamide, bis acrylamide, acrylamide compounds such as acetic acid; (3) divinyl benzene, divinyl ether, divinyl ethylene urea 乙烯基化合物;(4)邻苯二甲酸二烯丙酯、马来酸二烯丙酯、二烯丙基胺、三烯丙基胺、三烯丙基铵盐、季戊四醇的烯丙基醚化物、在分子中具有至少2个烯丙醚单元的スクロ-ゼ的烯丙醚化物等的聚烯丙基化合物;(5)(甲基)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、2-羟基-3-丙烯酰氧基丙基(甲基)丙烯酸酯等不饱和醇的(甲基)丙烯酸酯等。 Vinyl compounds; (4) diallyl phthalate, diallyl maleate, diallylamine, triallylamine, triallyl ammonium salts, allyl etherified pentaerythritol , su ku ro having at least two allyl ether units in the molecule - ease up allyl ether compounds such as polyallyl compound; (5) (meth) acrylate, vinyl (meth) acrylate, 2 - hydroxy-3-acryloyloxypropyl (meth) acrylate, (meth) acrylate unsaturated alcohols.

交联剂,相对全部单体和交联剂的合计100质量份,较好是0.1质量份以上,更好是3质量份以上,特别最好是10质量份以上,上限较好是75质量份以下,更好是60质量份以下,特别最好是55质量份以下。 A crosslinking agent, relative to 100 parts by total mass of all monomers and crosslinking agent is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, particularly preferably 10 parts by mass or more, the upper limit is preferably 75 parts by mass or less, more preferably 60 parts by mass, particularly preferably 55 parts by mass or less.

[复合聚合物粒子的制造方法]通过将用硅氧烷和/或氟化合物被覆的金属氧化物、含有溶解度参数不到8.9的乙烯基单体的单体成分和交联剂分散混合的过程(以下,称做过程1)、以及此后进行悬浮聚合的过程(以下,称做工序2)来制造本发明的复合聚合物粒子。 [Method for producing the composite polymer particles] The metal oxide by using a silicone and / or fluorine compound is coated, a solubility parameter of less than 8.9 containing vinyl monomer and a crosslinker dispersed monomer component mixing process ( hereinafter referred to as process 1), and thereafter the suspension polymerization process (hereinafter referred to as step 2) producing the composite polymer particles of the present invention.

在过程1中,用硅氧烷和/或氟化合物被覆的金属氧化物与单体成分(溶解度参数不到8.9的乙烯基单体、和根据需要含有8.9以上的单体)和联剂的质量比,较好是金属氧化物/单体成分和交联剂的合计量=25/75~90/10,最好是30/70~70/30。 In process 1, with a silicone and / or fluorine compound-coated metal oxide and the monomer component (vinyl monomer solubility parameter of less than 8.9, and if necessary a monomer containing more than 8.9) and mass linking agent ratio, preferably a metal oxide / total amount of monomer components and crosslinker = 25/75 ~ 90/10, preferably 30/70 ~ 70/30.

在乙烯基单体的分散中,为了提高分散效率,根据需要可以添加有机溶剂。 Vinyl monomers in the dispersion in order to improve dispersion efficiency, an organic solvent may be added if necessary. 作为这样的有机溶剂,例如可举出直链的或者环状的饱和烃系溶剂(正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、环己烷等)、直链的或者环状的不饱和烃系溶剂(甲苯、二甲苯等)、酮类有机溶剂(丙酮、甲基·乙基酮等)、酯系有机溶剂(乙酸乙酯、乙酸丁酯等)、直链的或者环状的聚二甲基硅氧烷等。 As such organic solvents, and examples thereof include straight-chain or cyclic saturated hydrocarbon solvents (n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane and the like) , straight-chain or cyclic unsaturated hydrocarbon solvents (toluene, xylene, etc.), a ketone organic solvent (acetone, methyl ethyl ketone, etc.), ester-based organic solvent (ethyl acetate, butyl acetate, etc. ), linear or cyclic polydimethyl siloxane.

在这里,在分散中使用均化器、高压均化器、超声波分散机、立式球磨机、球磨机、砂磨机等分散机。 Here, the dispersion in a homogenizer, high pressure homogenizer, an ultrasonic disperser, attritor mill, a ball mill, a sand mill dispersing machine and the like.

根据需要,在过程1中也可以添加在过程2中添加的分散·乳化剂。 If necessary, in process 1 may be added in the process of adding 2-emulsifier dispersion. 在添加的情况下,相对100质量份金属氧化物,最好添加1~30质量份。 In the case of added metal oxides with respect to 100 parts by mass, preferably 1 to 30 parts by mass was added. 分散时间最好是30分钟~5小时左右。 The dispersion time is preferably 30 minutes to 5 hours.

在过程2中,混合在过程1中得到的分散液和水、聚合引发剂、分散·乳化剂,进行乳化或者悬浮后,进行聚合。 In the process 2, and the aqueous mixed dispersion obtained in process 1, a polymerization initiator, dispersing and emulsifying agent, emulsification or suspension polymerization.

作为用于悬浮聚合的分散·乳化剂,可举出月桂基硫酸钠、鲸蜡基硫酸钠、聚氧乙烯月桂基醚硫酸钠、脂肪酸钠、烷基(甲基)牛黄酸钠等阴离子表面活性剂,除此之外,阳离子表面活性剂、非离子表面活性剂等低分子的表面活性剂;聚乙烯醇、聚乙烯基吡咯烷酮、羟乙基纤维素、羟丙基纤维素、明胶、淀粉、羧甲基纤维素、聚乙烯烷基醚等高分子分散剂;硫酸钡、硫酸钾、碳酸钡、碳酸钙、碳酸镁、磷酸钙等难水溶性无机盐。 As a dispersion-suspension polymerization emulsifiers include sodium lauryl sulfate, cetyl sulfate, sodium polyoxyethylene lauryl ether sulfate, fatty acid sodium, alkyl (meth) anionic surfactants such as sodium bezoar agents, in addition, cationic surfactants, nonionic surfactants and the like low molecular weight surfactants; polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, hydroxypropyl cellulose, gelatin, starch, carboxymethyl cellulose, polyvinyl alkyl ether polymer dispersant; barium sulfate, potassium sulfate, barium carbonate, calcium carbonate, calcium phosphate and other sparingly water-soluble inorganic salt. 相对在过程1中得到的100质量份分散液,最好添加0.1~20质量份的分散·乳化剂。 100 parts by mass of the dispersion obtained in process relative to 1, preferably 0.1 to 20 parts by mass dispersed and emulsifier.

作为聚合引发剂,虽然根据反应系决定,但过氧化物系引发剂可举出有机或无机过酸或其盐、偶氮二系化合物的单独或者和还原剂的组合而形成的氧化还原系的过氧化物。 As the redox polymerization initiator, though it determined depending on the reaction system, the peroxide initiator may be formed include an organic or inorganic peracid or a salt thereof, alone or in combination reducing agent and titanium-based azo compound is peroxide.

例如,可举出叔丁基过氧化物、叔戊基过氧化物、枯烯基过氧化物、过氧化乙酰、过氧化丙酰、过氧化苯甲酰(BPO)、过氧化苯甲酰基异丁酰、过氧化月桂酰(LPO)、叔丁基过氧化氢、环己基过氧化氢、过氧化四氢化萘、过乙酸叔丁酯、过苯甲酸叔丁酯、双(2-乙基己基过氧二碳酸酯)、2,2′-偶氮二异丁腈(AIBN)、2,2′-偶氮二异戊腈、2,2′-偶氮二(2-甲基丙腈)、苯基偶氮三苯基甲烷、2,2′-偶氮二(2-脒基丙烷)二盐酸盐、2,2′-偶氮二[2-(5-甲基-2-咪唑啉-2-基)丙烷]二盐酸盐、2,2′-偶氮二[2-(2-咪唑啉-2-基)丙烷]二盐酸盐、过硫酸钠、过硫酸钾、过硫酸铵、过氧化氢、过硫酸盐与三乙胺、三乙醇胺、二甲基苯胺等叔胺的组合等。 Examples thereof include t-butyl hydroperoxide, t-amyl peroxide, cumyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide (the BPO), benzoyl peroxide, isopropyl butyryl, lauroyl peroxide (of LPO), t-butyl hydroperoxide, cyclohexyl hydroperoxide, tetralin peroxide, t-butyl peracetate, t-butyl perbenzoate, bis (2-ethylhexyl peroxydicarbonate), 2,2'-azobisisobutyronitrile (of AIBN), 2,2'-azobis isovaleronitrile, 2,2'-azobis (2-methylpropionitrile) , phenylazo triphenylmethane, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-imidazole -2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, persulfates and triethylamine, triethanolamine, tertiary amines like dimethylaniline combination.

相对乙烯基单体和交联剂的合计量,聚合引发剂最好是0.1~5质量%。 Relative to the total amount of vinyl monomer and a crosslinking agent, a polymerization initiator is preferably 0.1 to 5% by mass. 聚合开始温度最好是20~95℃,进行聚合的时间最好是3~48小时。 The polymerization initiation temperature is preferably 20 ~ 95 ℃, the polymerization time is preferably 3 to 48 hours.

如上所述,按照如上述的公知方法使用用硅氧烷和/或氟化合物被覆的金属氧化物、含有溶解度参数不到8.9的乙烯基单体的单体成分和交联剂分散或者悬浮在水中,而形成液滴,通过进行聚合反应就能够制造作为目的的复合聚合物粒子。 As described above, using a metal oxide with a silicone and / or fluorine compounds coated according to the known method as described above, a monomer component containing a vinyl monomer and a crosslinking agent solubility parameter of less than 8.9 are dispersed or suspended in water to form droplets, the polymerization reaction can be performed by producing the composite polymer particles as the object.

聚合后,用过滤或离心分离等将复合聚合物粒子进行固液分离,去除水相,根据需要进行水洗,通过减压干燥、喷雾干燥、冷冻干燥等通常手段,就能够作为粉体离析。 After the polymerization, by filtration or centrifugation, etc. The composite polymer particles to solid-liquid separation, the aqueous phase is removed, washed with water if necessary, by vacuum drying, spray drying, freeze drying or the like means usually, can be isolated as a powder. 并根据需要,进行凝集物的粉碎。 And, if necessary, pulverization of agglomerates. 作为粉碎的方法,可以使用喷射粉碎机、滚柱磨机(ピンミル)、细磨机(コ-ミル)、锤磨机、水平运动磨机等干式法,管道混合器(ラインミキサ-)、分散机、均化器、マイルダ-、高速混合器等湿式法。 As a pulverization method, a jet mill, roller mill (ピ nn this mill), fine mill (U - this mill), a hammer mill, horizontal movement mill or a dry method, a line mixer (LITE nn Chemie Ink sa -), dispersing machine, a homogenizer, microspheres were Hikaru the inter -, wet process such as a high speed mixer.

[微粒子金属氧化物(A)]在本发明的紫外线防御化妆品中使用的3种粉体中,第1粉体是一次粒子的平均粒径为0.001~0.1μm,具有紫外线防御能力和可见光的透过性的微粒子金属氧化物(以下,作为微粒子氧化物)。 [Metal oxide fine particles (A)] 3 Species UV protection powder used in the cosmetic of the present invention, the first powder is the average primary particle size of 0.001 ~ 0.1μm, an ultraviolet and visible through defenses over fine particles of the metal oxide (hereinafter, fine particles as oxide). 在这里,一次粒子的形状,除圆球状之外,也包括椭圆形,还包括在粒子表面具有凹凸的形状等,在不是圆球状的情况下,粒径的长径和短径的比是3以下。 Here, the shape of the primary particles, in addition to the spherical, including an oval, further comprising a concavo-convex shape on the surface of particles, in the case of not spherical, the particle diameter ratio of long diameter and short diameter is 3 the following. 另外,所谓具有紫外线防御能力是指,具有吸收或者散射领域为280~400nm范围的紫外线,尤其280~340nm的UVB、UVAII的效果。 Further, the term refers to having a UV protection ability, an ultraviolet absorbing or scattering field in a range of 280 ~ 400nm, UVB 280 ~ 340nm in particular, the effect of UVAII. 再有,所谓具有可见光的透过性是在皮肤上以1mg/cm2的涂布量涂布在硅中分散5质量%粉体的分散液时,具有不发生留白的透明性,最好即使在粉体10质量%硅分散液中,也具有不发生留白的透明性。 Note that when the so-called visible light having a permeability to the coating amount is 1mg / cm2 of coating dispersion 5% by mass dispersion of the powder in the silicon on the skin blank having transparency does not occur, even if the best 10% by mass of silicon powder in the dispersion liquid, also has transparency does not occur in the blank.

微粒子氧化物的一次粒子的平均粒径,从涂布时的使用感这点考虑,是0.001μm以上,更好是0.005μm以上,特别最好是0.01μm以上。 The average primary particle size of the fine oxide coating from feeling upon this consideration, is 0.001μm or more, and more preferably 0.005μm or more, particularly preferably 0.01μm or more. 另外,该平均粒径,从涂布化妆品时的透明性的这点考虑,是0.1μm以下,更好是0.08μm以下,特别最好是0.06μm以下。 Further, the average particle diameter, from this point of transparency of the coating when the cosmetic is 0.1μm or less, preferably 0.08μm or less and particularly preferably 0.06μm or less. 再者,在本发明中,平均粒径是指用电子显微镜照片测定的粒径的平均值。 Further, in the present invention, the average particle diameter means an average value measured by an electron microscope photograph of the particle diameter.

本发明的微粒子氧化物是具有吸收或者散射UVB至UVAII的广泛范围的效果的金属氧化物。 Fine oxide of the present invention is a metal oxide to absorb or scatter UVB UVAII wide range of effects. 尤其,从吸收或者散射紫外线的效果高这点考虑,最好是选自氧化锌、氧化钛和氧化铈的1种或者2种以上。 In particular, this high from the viewpoint of absorbing or scattering ultraviolet light effect, more preferably selected from zinc oxide, titanium oxide and cerium oxide, either alone or in combination.

作为微粒子氧化物的市场上出售品,例如微粒子氧化锌,可举出FINEX-25、FINEX-50、FINEX-75(以上,堺化学(株));MZ500系列、MZ2700系列(以上,テイカ(株));ZnO-350(以上,住友大坂セメント(株))等。 Sold as goods on the market fine oxides, such as particles of zinc oxide include FINEX-25, FINEX-50, FINEX-75 (the foregoing, manufactured by Sakai Chemical (Co.)); MZ500 Series, MZ2700 series (all manufactured by Tayca (strain )); ZnO-350 (the foregoing, manufactured by Sumitomo Osaka ã me nn Suites (Ltd.)) and the like. 作为微粒子氧化钛,可举出TTO-55系列、TTO-51系列(以上,石源产业(株));JR系列、JA系列(以上,テイカ(株))等。 As the titanium oxide fine particles include TTO-55 Series, TTO-51 Series (or more, stone industry source (Ltd.)); the JR series, JA series (all manufactured by Tayca (Ltd.)) and the like. 另外,作为微粒子氧化铈,可举出包括由ニツキ公司或者イミケミカル公司出售的高纯度氧化铈。 Further, as the cerium oxide particles may include high-purity cerium oxide comprising Ni, sold by the company or イ tsu Ink Chemicals Co. Chemie company. 其中,尤其以氧化锌或者氧化钛为最佳。 Wherein, in particular, zinc oxide or titanium oxide is preferred.

另外,微粒子氧化物的表面,为了提高在化妆品中的分散性、提高其紫外线防御效果和透明性,最好使用已进行在通常化妆品用粉体上实施的表面处理的。 Further, the surface of the oxide particles, to improve the dispersibility in cosmetics, UV-shielding effect and improve the transparency, it is preferable to use a surface has been used in the usual cosmetic powder embodiments of the process.

作为处理的方法,可举出利用甲基氢化二烯聚硅氧烷、二甲基聚硅氧烷、利用硅树脂等的处理方法、利用阴离子表面活性剂、阳离子表面活性剂等表面活性剂的处理方法、利用尼龙、聚甲基丙烯酸甲酯、聚乙烯、特氟隆、聚氨基酸等高分子的处理方法、利用含有全氟基化合物、卵磷脂、胶原、金属皂、亲油性蜡、多元醇的部分酯化物或者完全酯化物等的处理方法。 As a method of treatment may include the use of methylhydrogen polysiloxane, dimethylpolysiloxane, treatment with a silicon resin or the like, using an anionic surfactant, a cationic surfactant of the surfactant processing method using a nylon, polymer processing method of polymethyl methacrylate, polyethylene, Teflon, poly amino acids, using a perfluoro group-containing compound, lecithin, collagen, metal soap, lipophilic wax, polyalcohol the processing method of partially esterified or completely esterified product and the like.

微粒子氧化物的处理量,从紫外线防御效果这点考虑,相对微粒子氧化物是0.1~20质量%,特别最好是1~10质量%。 Processing amount oxide fine particles, ultraviolet shielding effect this in mind, the oxide fine particles is opposite from 0.1 to 20 mass%, particularly preferably 1 to 10 mass%.

进而,微粒子氧化物,可以以粉末本身、油剂分散物等提供,如果配合在化妆品中时分散性良好,可以以任何的状态提供。 Further, the oxide fine particles, may be powder itself, provide oil dispersion, if with good dispersibility in a cosmetic, may be provided in any state. 作为油剂分散物或者水分散物进行配合时,预先使微粒子氧化物的粉体进行高分散,使用具有高分散的微粒子氧化物的粉体,紫外线防御效果和可见光的透过性会变得更高,作为结果,提高化妆品的紫外线防御效果和可见光的透明性,因此使用这些微粒子氧化物的高分散物(以下,作为微粒子高分散体),或者最好组合微粒子高分散体和粉末状的微粒子氧化物而使用。 When fitted as an oil dispersion or aqueous dispersion, previously the powder is highly dispersed oxide particles, using an oxide powder of fine particles having a high dispersion, and ultraviolet protection effect becomes more visible transmittance high, as a result, to improve the ultraviolet protection effect of cosmetic and transparency to visible light, so a high dispersion of these oxide particles (hereinafter, fine particles of a high-dispersion), or preferably a combination of high fine particle dispersion of the fine particles and powdered oxide is used.

作为微粒子高分散体,例如可举出在特开平8-12961号公报、特开平9-100112号公报、特开平11-131048号公报、特开平2000-290156号公报等中记载的超微粒子分散体。 As the fine particles of high dispersion, can for example include in JP-8-12961, JP-A No. 9-100112, JP-A No. 11-131048, JP Patent Publication No. 2000-290156 and the like nanoparticles described dispersion .

[薄片状氧化锌(B)]在本发明的紫外线防御化妆品中使用的形状不同的粉体中,第2粉体是平均大小为0.1μm~1μm、平均厚度为0.01μm~0.2μm的薄片状氧化锌。 [Flaky zinc oxide (B)] different shapes used in the ultraviolet protection cosmetics of the present invention, the powder, the second powder having an average size of 0.1μm ~ 1μm, the average thickness of a sheet of 0.01μm ~ 0.2μm Zinc oxide. 通过使用薄片状氧化锌,尤其长波长UVAI(340nm~400nm)下的散射效果提高,因此显示良好的紫外线防御效果。 By using a sheet of zinc oxide, in particular under the effect of scattering long wavelength UVAI (340nm ~ 400nm) increase, thus indicating good UV protection effect.

在这里,所谓薄片状氧化锌的平均大小和平均厚度,是分别用电子显微镜照片测定的面积方向的平均粒径和平均厚度。 Here, the average thickness and average size of the so-called flaky zinc oxide, average particle diameter and the average thickness is the area of ​​direction are determined by an electron micrograph.

从发生凝集而不降低分散性这点考虑,平均大小是0.1μm以上,从透明性和紫外线吸收性高这点考虑,是1μm以下,但更好是0.1μm~0.8μm,特别最好是0.2μm~0.7μm。 Without reducing the dispersibility of agglutination from the viewpoint of this, the average size is over 0.1 m, transparency and high UV absorbing this in mind, is 1μm or less, but more preferably 0.1μm ~ 0.8μm, particularly preferably 0.2 μm ~ 0.7μm. 从薄片状形态难以崩溃这点考虑,平均厚度是0.01μm以上,从使用感良好这点考虑,是0.2μm以下,但更好是0.01μm~0.1μm,特别最好是0.01μm~0.05μm。 It is difficult to form a sheet from the collapse of this consideration, the average thickness is 0.01 m or more, from the viewpoint of good feeling of use this is 0.2μm or less, but more preferably 0.01μm ~ 0.1μm, particularly preferably 0.01μm ~ 0.05μm.

从提高透明性这点考虑,薄片状氧化锌的长宽比,较好是3以上,更好是5以上,特别最好是7以上。 Improving the transparency of this consideration, the aspect ratio of the flaky zinc oxide is preferably 3 or more, preferably 5 or more, particularly preferably 7 or more. 在这里,长宽比是指按照平均大小/平均厚度求出的值。 Here, the aspect ratio refers to a value according to the average size / average thickness obtained.

作为本发明的薄片状氧化锌,最好是相对100摩尔锌还含有0.005~1.0摩尔的+2价以上的金属元素,由此而提高透明性的薄片状氧化锌。 As the flaky zinc oxide of the present invention, relative to 100 mol of zinc preferably further contains at least 0.005 to 1.0 mole of divalent metal element, thereby improving the flaky zinc oxide transparency. 以+2价以上的金属元素结合并保持在成为母粒子的薄片状氧化锌的表面或者其内部的状态为佳。 At least divalent metallic element to become bound and held on the surface of the flaky preferably zinc oxide particles, or a mother's internal state.

作为+2价以上的金属元素,可举出铁、锆、钙、锗、锰、镁、钇等,这些金属元素可以使用1种或者可以组合2种以上使用。 As a valence of +2 or more metal elements include iron, zirconium, calcium, germanium, manganese, magnesium, yttrium, these metal elements may be used alone or in combination of two or more thereof. 就是这些金属元素之中。 Is that these metal elements into. 从紫外线的防御效果高来看,以铁、锆、镁为佳。 High ultraviolet protection effect from the point of view, iron, zirconium and magnesium are preferred. 另外,在组合这些金属元素使用时,最好是锆和铁、锆和镁、铁和镁、铁和钙、镁和锗的组合。 Further, when using a combination of these metal elements, preferably zirconium, and zirconium, iron, magnesium, iron and combinations magnesium, iron and calcium, magnesium and germanium.

+2价以上的金属元素的含量,从提高紫外线防御性这点考虑,相对100摩尔薄片状氧化锌粉末的锌量,是0.005摩尔以上,最好是0.01摩尔以上。 Content of divalent or more metal elements, which point from the viewpoint of improved UV protection, the amount of zinc oxide relative to 100 mol of the flaky zinc powder, not less than 0.005 mole, preferably 0.01 mole or more. 另外,从良好的紫外线防御性这点考虑,是1.0摩尔以下,最好是0.5摩尔以下。 Further, from the good UV protection consideration of this point, it is 1.0 mol or less, preferably 0.5 mol or less. +2价以上的金属元素的含量,可以在溶解含有金属元素的酸或者碱液中溶解粉末,使用IPC发光分析等求出。 The content of the above divalent metal element, a powder may be dissolved in an acid or alkaline solution containing a dissolved metal element, an IPC emission analysis is obtained.

另外,薄片状氧化锌的表面,为了提高化妆品中的分散性,最好使用实施表面处理的表面。 Further, the surface of the flaky zinc oxide, in order to improve the dispersibility of the cosmetic, it is preferable to use a surface-treated surface. 作为表面处理的方法,可以使用在上述微粒子金属氧化物的表面处理中使用的方法。 As a method of surface treatment, it can be used in the method of surface treatment of the above-described fine metal oxide. 利用薄片状氧化锌的表面处理剂的处理量,从得到良好的紫外线防御性效果这点来看,相对薄片状氧化锌是0.1~20质量%,特别最好是1~10质量%。 Zinc oxide using a sheet processing amount of the surface treating agent, from the ultraviolet to obtain a good defensive effect this point of view, relative to the flaky zinc oxide is 0.1 to 20 mass%, particularly preferably 1 to 10 mass%.

作为本发明的薄片状氧化锌,例如可举出在特开平1-175921号公报、特开平1-230431号公报、特开平8-12526号公报、特开平9-137152号公报等中记载的薄片状氧化锌。 As the flaky zinc oxide of the present invention include, for example in JP-1-175921, JP-A No. 1-230431, JP-A No. 8-12526, JP-A No. 9-137152 and the like sheet described in JP like zinc oxide.

[化妆品]作为能够配合本发明的复合聚合物粒子的化妆品,如果是能够发挥紫外线遮蔽效果、皮肤隐蔽效果,就能够配合在通常的化妆品中。 [Cosmetics] As can be complex composite polymer particles of the present invention is a cosmetic, if it is able to play an ultraviolet shielding effect, skin concealment, it is possible to fit a conventional cosmetics. 具体地说,粉底、胭脂、眼影膏、睫毛油、眼线膏、画眉、口红、指甲油等化妆用化妆品,遮阳光化妆品,底层化妆品是令人满意的。 Specifically, foundation, rouge, eye shadow, mascara, eyeliner, thrush, lipstick, nail polish, and other cosmetics, makeup, sun cosmetic cover, the bottom is satisfactory cosmetic. 化妆品中的复合聚合物粒子的含量,较好是0.1~60质量份,最好是1~40质量份。 Content of the composite polymer particles in cosmetics, preferably from 0.1 to 60 parts by mass, preferably 1 to 40 parts by mass.

进而在化妆品中,作为通常的化妆品用原料使用的其他成分,例如可以适当选择白色颜料(氧化钛等)、体质颜料(云母、滑石粉、绢云母、硫酸钡等)、着色颜料(氧化铁红、氧化铁黄、氧化铁黑、黄色401号、红色226号、胶囊化有色颜料、有机色素等)、珠光颜料、天然矿物、有机粉末、油剂(凡士林、精制羊毛脂、纯地蜡、橄榄油、霍霍巴油、蓖麻油、角鲨烷、液体石蜡、酯油、甘油二酯、甘油三酯、硅油、全氟聚醚、氟改性硅油等)、紫外线防御剂、凝胶化剂、蜡(微晶蜡、高级脂肪酸或高级醇等固体·半固体油分等、金属皂、表面活性剂、保湿剂、防腐剂、香料、增稠剂、防氧化剂、杀菌剂、抗汗剂、其他各种添加剂进行配合。 Further, in cosmetics, as other ingredients commonly used cosmetic raw material, for example, suitably selected white pigment (titanium oxide), extender pigments (mica, talc, sericite, barium sulfate, etc.), a coloring pigment (red iron oxide , iron oxide yellow, iron oxide black, yellow No. 401, red No. 226, encapsulated colored pigment, organic dye, etc.), pearlescent pigments, natural mineral, organic powders, oils (petrolatum, purified lanolin, ceresin, olives oil, jojoba oil, castor oil, squalane, liquid paraffin, ester oils, diglycerides, triglycerides, silicone oils, perfluoropolyether, a fluorine modified silicone oil), UV protection agents, gelling agents, wax solids and semi-solid oil components (a microcrystalline wax, higher fatty acid or higher alcohol, a metal soap, surfactants, humectants, preservatives, perfumes, thickeners, antioxidants, bactericides, anti-perspirants, various other additives were blended.

本发明的化妆品以固体化妆品、蜡化妆品、乳液(水包油型、油包水型)化妆品、液体化妆品、凝胶化妆品等制品形态使用。 Cosmetic of the present invention in solid cosmetic, the cosmetic wax product form, emulsions (oil in water, water in oil) cosmetics, liquid cosmetics, gel cosmetics use.

在本发明中,第一的微粒子金属氧化物和包含在第三的内包聚合物粒子中的微粒子金属氧化物的总量与第二的薄片状氧化锌的配合比,从兼顾对UVA的充分防御效果和作为化妆品涂布时的白度不强、确保充分的透明性来看,相对微粒子金属氧化物的总量,薄片状氧化锌较好是0.005~0.4的质量比。 In the present invention, the blending ratio of the total amount of the first metal oxide particles and fine particles of metal oxides contained in the third pack of the polymer particles and the second sheet-like zinc oxide, both fully from the defense against UVA when the whiteness and the effect as a cosmetic coating is not strong, to ensure sufficient transparency view, the relative amount of metal oxide particles, the flaky zinc oxide is preferably from 0.005 to 0.4 mass ratio. 进而最好是0.05~0.2的质量比。 Further mass ratio is preferably 0.05 to 0.2.

像这样,由于组合使用粒子形状是大致粒状、具有遍及UVB至UVAII的广泛范围的紫外线防御剂能力和可见光的透过性的微粒子金属氧化物,是薄片状、从UVAII至近似可见光的UVAI的散射效果高的氧化锌和内包微粒子金属氧化物的聚合物粒子,就能够效率良好地提高紫外线防御性效果,而且能够得到透明性和使用感优良的化妆品。 Thus, since the particle shape is generally a combination of granular, fine particles of metal oxide having a permeability over a wide range of UVB to UVAII ability of the ultraviolet light protection and visible light, is a sheet, the scattering of visible light from UVAII to approximately the UVAI the effect of zinc oxide and high polymer encapsulated particles of metal oxide fine particles, it is possible to efficiently increase the effect of the ultraviolet protection, and can obtain an excellent transparency and cosmetic use feeling.

在本发明的化妆品中,更由于配合有机紫外线吸收剂,能够更加提高紫外线防御效果。 In the cosmetic of the present invention, since more organic UV absorbers, UV-shielding effect can be further enhanced. 作为所使用的有机紫外线吸收剂,没有特别的限制,油溶性、水溶性的都能够适合使用。 Examples of the organic ultraviolet absorber used is not particularly limited, and an oil-soluble, water-soluble can be suitably used.

在化妆品中的紫外线吸收剂的配合量,由于剂型等不同而不同,但从提高外线防御效果这点考虑,在全组成中,较好是0.1~25.0质量%,最好是0.5~10.0质量%。 The amount of the ultraviolet absorber in cosmetics and the like since the dosage varies, but improved protective effect outside this in mind, in the whole composition, preferably from 0.1 to 25.0% by mass, preferably 0.5 to 10.0% by mass . 紫外线吸收剂的配合量,如果是上述范围内,在充分提高紫外线防御效果的同时,油性感不变强,使用感也良好,是令人满意的。 The amount of the ultraviolet absorber, if it is within the above range, while sufficiently improving the ultraviolet protection effect, the same strong oily feel, good sense of use, is satisfactory.

另外,对于本发明的化妆品来说,在通常化妆品用中使用的成分,例如可以使用液体油、固体脂(蜡)、半固体油、醇类、水、保湿剂、水溶性高分子、油溶性高分子、高分子胶乳、各种表面活性剂、药剂、植物提取液、N-脂酰基鞘氨醇类、血液循环促进剂、冷感剂、抗汗剂、杀菌剂、皮肤赋活剂、pH调整剂、增稠剂、防氧化剂、防腐剂、香料等。 Further, the cosmetic of the present invention, in the cosmetic ingredients typically used in, for example, liquid oils, solid fat (waxes), semisolid oils, alcohols, water, humectants, water-soluble polymers, oil-soluble polymers, polymer latexes, various surfactants, drugs, plant extracts, N- acyl sphingosine, blood circulation accelerators, cooling agent, antiperspirants, bactericides, skin activators, pH adjusting agents, thickeners, antioxidants, preservatives, perfumes and the like.

本发明的化妆品,作为附加紫外线防御性的各种化妆品,例如作为皮肤护理化妆品、化妆用化妆品、头发化妆品等使用。 Cosmetic of the present invention, as an additional ultraviolet defensive various cosmetics such as a skin care cosmetic, makeup cosmetic use, hair cosmetics. 另外,本发明的剂型,可举出粉末状、粉末固体状、水中油型乳化状、洗剂状、油性固体状、油性液体状、膏状、多层状、凝胶状等。 In addition, dosage forms of the present invention include powders, solid powders, oil in water type emulsified, lotion like, oily solid, oil liquid, paste, multilayer, or gel. 尤其,作为化妆用化妆品,可举出防晒黑化妆品、粉底、白粉、化妆底层、胭脂、口红、コンシ-ラ-、眼制品等。 In particular, as a makeup cosmetic include black sunscreen cosmetics, foundation, white powder, makeup bottom, rouge, lipstick, Nikon Corporation Silicone - ra -, eye products.

为了发挥紫外线防御能力,需要满足金属氧化物在复合聚合物粒子中具有相当的有效量、均匀的分散以及在配合组成中复合聚合物粒子均匀的分散的2个条件。 In order to play UV protection ability, to meet the needs of a metal oxide having a relatively effective amount composite polymer particles, in a uniform dispersion and uniform composition with the two conditions of the composite particles dispersed in the polymer. 通常,如果高浓度配合表面未处理的金属氧化物,就会吸收单体,而丧失流动性,不能进行乳化,但在本发明中,由于使用用平均粒径是1μm以下的硅氧烷和/或氟化合物被覆的金属氧化物、及溶解度参数不到8.9的单体,就能够使相当量的金属氧化物较均匀地分散在复合聚合物粒子中,流动性良好,能够进行乳化。 Typically, if a high concentration of the metal oxide surface-untreated, will absorb the monomer, the fluidity is lost, it can not be emulsified, but in the present invention, since the average particle size is 1μm or less and silicone / or fluorine compound-coated metal oxide, and the solubility parameter of the monomer is less than 8.9, it is possible to make a considerable amount of the metal oxide more uniformly dispersed in the composite polymer particles, good fluidity, can be emulsified. 而且也能够稳定地配合在化妆品中,因此配合本发明的复合聚合物粒子的化妆品,紫外线防御性能力高,使用感也良好。 Further it is possible to stably fit in a cosmetic, the cosmetic thus with the composite polymer particles of the present invention, high ultraviolet protection capabilities, feeling of use was good.

本发明的化妆品,由于组合使用具有特定的平均粒径且具有从UVB至UVAII的紫外线防御效果和可见光的透过性的金属氧化物、从UVAII至近似可见光的UVAI的散射效果高的薄片状氧化锌、以及紫外线防御效果高且使用感良好的特定粒径的微粒子金属氧化物内包聚合物粒子,因此具有高的紫外线防御效果,特别高的长波长紫外线防御效果,透明性高,而且使用感也良好。 Cosmetic of the present invention, since a combination having a specific average particle size and having from UVB ultraviolet protection effect of a metal oxide to UVAII permeable to visible light, a high scattering effect of visible light from UVAII to approximately flaky oxide UVAI fine metal oxide particles with a high polymer encapsulated zinc, and an ultraviolet shielding effect and good feeling in use of a specific particle size, thus having a high ultraviolet protection effect, particularly high long-wavelength ultraviolet shielding effect, high transparency, and the sense of use good.

附图的简要说明图1是在实施例1得到的复合聚合物粒子的扫描电子显微镜照片。 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron micrograph of composite polymer particles obtained in Example 1 in the embodiment.

图2是在实施例1得到的复合聚合物粒子的透射电子显微镜照片。 FIG 2 is a transmission electron micrograph of composite polymer particles obtained in Example 1.

图3是在比较例1得到的复合聚合物粒子的扫描电子显微镜照片。 FIG. 3 is a scanning electron micrograph of composite polymer particles obtained in Comparative Example 1.

图4是在比较例1得到的复合聚合物粒子的透射电子显微镜照片。 FIG 4 is a transmission electron micrograph of composite polymer particles obtained in Comparative Example 1.

图5是在比较例2得到的复合聚合物粒子的扫描电子显微镜照片。 FIG 5 is a scanning electron micrograph of Comparative Example 2 composite polymer particles obtained.

图6是在比较例2得到的复合聚合物粒子的透射电子显微镜照片。 Comparative Example 6 is a transmission electron micrograph of composite polymer particles obtained.

具体的实施方式实施例实施例1使用玻璃珠磨机,在45g甲基丙烯酸月桂酯(SP值8.7)、45g乙二醇二甲基丙烯酸酯中将60gテイカ制硅处理氧化锌(MZ-507S)搅拌3小时(用大电子制ELS-8000测定的氧化锌的平均粒径是0.3μm)。 EXAMPLES Example 1 using a glass bead mill, lauryl acrylate (SP value 8.7) in methyl 45g, 45g of ethylene glycol dimethacrylate in the ester 60g Tayca prepared silicon treated zinc oxide (MZ-507S specific embodiment ) was stirred for 3 hours (average particle diameter of zinc oxide was measured with a large  ELS-8000 manufactured by electronic is 0.3μm). 此后,加入3g过氧化月桂酰。 Thereafter, 3g lauroyl peroxide. 在1500g离子交换水中溶解20g月桂基硫酸钠,加入上述的氧化锌浆中,使用マイルダ-进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是1.6μm)。 1500g of ion-exchanged water was dissolved in 20g sodium lauryl sulfate, was added to the zinc oxide slurry, using microspheres were Hikaru the inter - dispersion (produced by Horiba LA-910 prepared emulsion was measured an average particle size 1.6μm). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至70℃,在70℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行10小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 70 ℃, maintained at 70 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 10 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到120g复合聚合物粒子(氧化锌的内包率40质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to give 120g of composite polymer particles (encapsulated by mass of zinc oxide, 40%).

所得到的复合聚合物粒子的扫描电子显微镜照片示于图1中,透射电子显微镜照片示于图2中。 A scanning electron micrograph of the composite particles of the obtained polymer is shown in FIG. 1, a transmission electron microscope photograph is shown in Fig.

实施例2使用玻璃珠磨机,在45g甲基丙烯酸十八酯(SP值8.7)、45gl,6-己二醇二甲基丙烯酸酯、30g庚烷中将90gテイカ制硅处理氧化锌(MZ-507S)搅拌3小时(用大电子制ELS-8000测定的氧化锌的平均粒径是0.4μm)。 Example 2 mill using glass beads, at 45g stearyl methacrylate (SP value 8.7), 45gl, 6- hexanediol dimethacrylate, 30g 90g heptane in the alkoxy Tayca prepared silicon treated zinc oxide (MZ -507S) was stirred for 3 hours (average particle diameter of zinc oxide was measured with a large  ELS-8000 manufactured by electronic is 0.4μm). 此后,加入3g过氧化月桂酰。 Thereafter, 3g lauroyl peroxide. 在1500g离子交换水中溶解15g椰油基甲基牛黄酸钠,加入上述的氧化锌浆中,使用均化器进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是1.6μm)。 1500g of ion-exchanged water was dissolved in 15g of sodium cocoyl methyl taurine, zinc oxide added to the slurry, dispersed using a homogenizer (average particle diameter of the emulsion was measured using LA-910 manufactured by Horiba Ltd. is 1.6μm ). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至70℃,在70℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行10小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 70 ℃, maintained at 70 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 10 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到120g复合聚合物粒子(氧化锌的内包率50质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to give 120g of composite polymer particles (encapsulated by mass of zinc oxide, 50%).

实施例3使用玻璃珠磨机,在30g甲基丙烯酸月桂酯(SP值8.7)、30g乙二醇二甲基丙烯酸酯中将40gテイカ制硅处理氧化锌(MZ-507S)搅拌3小时(用大电子制ELS-8000测定的氧化锌的平均粒径是0.3μm)。 Example 3 mill using glass beads, lauryl acrylate (SP value 8.7) in methyl 30g, 30g of ethylene glycol dimethacrylate in the ester 40g Tayca prepared silicon treated zinc oxide (MZ-507S) was stirred for 3 hours (with the average particle diameter of zinc oxide ELS-8000 assay of  electronic brake is 0.3μm). 此后,加入1.5g 2,2′-偶氮二-2,4-二甲基戊腈。 Thereafter, 1.5 g 2,2'-azobis-2,4-dimethylvaleronitrile. 在500g离子交换水中溶解30g聚乙烯醇(日本合成化学工业制EG-30)、1g硬脂酰基甲基牛黄酸钠,加入上述氧化锌浆中,使用マイルダ-进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是2.0μm)。 Was dissolved in 500g of ion-exchanged water, 30g of polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. EG-30), 1g sodium stearoyl methyl taurine, zinc oxide added to the slurry, using microspheres were Hikaru the inter - dispersion (manufactured by Horiba, Ltd. the average particle diameter of the emulsion measured by LA-910 was 2.0μm). 接着,将该分散液装入1000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至60℃,在60℃保持2小时,再升温至80℃,在80℃在氮气气氛下进行4小时聚合。 Subsequently, the dispersion was charged in a separable 1000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 60 ℃, maintained at 60 ℃ 2 hours and then warmed to 80 ℃, at 80 deg.] C in a nitrogen for 4 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到90g复合聚合物粒子(氧化锌的内包率40质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to obtain 90g of polymer composite particles (encapsulated by mass of zinc oxide, 40%).

实施例4使用玻璃珠磨机,在56g甲基丙烯酸月桂酯(SP值8.7)、19g乙二醇二甲基丙烯酸酯中将50g硅处理氧化钛(平均粒径0.25μm的氧化钛(石原产业制,CR-50),使用甲基氢化二烯聚硅氧烷(相对氧化钛2质量%)进行拒水处理)搅拌3小时(用大电子制ELS-8000测定的氧化钛的平均粒径是0.3μm)。 4 embodiment mill using glass beads, lauryl acrylate (SP value 8.7) in methyl 56g, 19g of ethylene glycol dimethacrylate in the 50g silicon-treated titanium oxide (average particle size 0.25μm titanium oxide (Ishihara Sangyo Example Ltd., CR-50), using the average particle diameter of methylhydrogen polysiloxane (relative to 2 mass% of titanium oxide) is water-repellent) was stirred for 3 hours (with a large measurement system ELS-8000 electron  titanium oxide is 0.3μm). 此后,加入1.5g过氧化月桂酰。 Thereafter, 1.5g of lauroyl peroxide. 在750g离子交换水中溶解7.5g聚乙烯醇(日本合成化学工业制EG-30),加入上述的氧化钛浆中,使用均化器进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是11.5μm)。 In 750g of ion-exchanged water was dissolved 7.5g of polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. EG-30), added to the above slurry of titanium oxide, dispersed using a homogenizer (manufactured by Horiba LA-910 manufactured by the emulsion is measured The average particle size was 11.5μm). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以150r/min搅拌,一边升温至75℃,在75℃在氮气气氛下进行8小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 150r / min stirring, the temperature was raised to 75 ℃, polymerized for 8 hours under nitrogen atmosphere at 75 ℃. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到120g复合聚合物粒子(氧化锌钛内包率40质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to give 120g of composite polymer particles (zinc oxide with titanium packet of 40 mass%).

实施例5使用玻璃珠磨机,在10g聚二甲基甲硅烷氧基丙基甲基丙烯酸酯(チツソ公司制,サイラプレ-ンFM0711,MW1000,SP值7.6)、50g甲基丙烯酸异十八酯(SP值8.2)、40g乙二醇二甲基丙烯酸酯、10g聚二甲基硅氧烷(5000cs)中将50g石原产业制的硅处理氧化钛(平均粒径0.25μm的氧化钛(石原产业制,CR-50),使用甲基氢化二烯聚硅氧烷(相对氧化钛2质量%)进行拒水处理)搅拌3小时(用大塚电子制ELS-8000测定的氧化钛的平均粒径是0.4μm)。 Example 5 mill using glass beads, at 10g polydimethyl butyldimethylsilyloxy propyl methacrylate (manufactured by Chisso Corporation, Cytec ra pu Rayon - nn FM0711, MW1000, SP value 7.6), 50g stearyl methacrylate, isobutyl (SP value 8.2), 40g of ethylene glycol dimethacrylate, 10g of polydimethylsiloxane (5000cs) manufactured by Ishihara Sangyo 50g in the silicon-treated titanium oxide (average particle diameter of 0.25μm titanium oxide (Ishihara Sangyo Ltd., CR-50), using methylhydrogen polysiloxane (relative to 2 mass% of titanium oxide) is water-repellent) was stirred for 3 hours (average particle diameter of titanium oxide is measured by Otsuka Electronics ELS-8000 is manufactured by 0.4μm). 此后,加入3g过氧化月桂酰。 Thereafter, 3g lauroyl peroxide. 在1500g离子交换水中溶解45g聚乙烯醇(日本合成化学工业制EG-30),加入上述的氧化钛浆中,使用均化器进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是1.8μm)。 Was dissolved in 1500g of ion-exchanged water, 45g of polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. EG-30), added to the above slurry of titanium oxide, dispersed using a homogenizer (manufactured by Horiba LA-910 emulsion system measured average particle size is 1.8μm). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至70℃,在70℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行10小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 70 ℃, maintained at 70 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 10 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到120g复合聚合物粒子(氧化锌钛内包率31质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to give 120g of composite polymer particles (zinc oxide with titanium packet rate 31 mass%).

比较例1使用玻璃珠磨机,在60g苯乙烯(SP值9.2)、30g二乙烯基苯中将60gテイカ制的硅处理氧化锌(MZ-507S)搅拌3小时(用大塚电子制ELS-8000测定的氧化锌的平均粒径是0.3μm)。 Comparative Example 1 using a glass bead mill, in the styrene 60g (SP value 9.2), the silicon-treated zinc oxide will 30g divinyl benzene, manufactured by Tayca 60g (MZ-507S) was stirred for 3 hours (manufactured by Otsuka Electronics ELS-8000 the average particle diameter of zinc oxide was measured 0.3μm). 此后,加入3g过氧化月桂酰。 Thereafter, 3g lauroyl peroxide. 在1500g离子交换水中溶解20g月桂基硫酸钠,加入上述的氧化锌浆中,使用マイルダ一进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是2.1μm)。 1500g of ion-exchanged water was dissolved in 20g sodium lauryl sulfate, was added to the zinc oxide slurry using a Hikaru the inter microspheres were dispersed (produced by Horiba LA-910 manufactured by an emulsion average particle size is measured 2.1μm). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至70℃,在70℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行10小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 70 ℃, maintained at 70 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 10 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到110g复合聚合物粒子(氧化锌的内包率40质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to give 110g of composite polymer particles (encapsulated by mass of zinc oxide, 40%).

得到的复合聚合物粒子的扫描电子显微镜照片示于图3中,透射电子显微镜照片示于图4中。 The obtained scanning electron micrograph of the composite polymer particles are shown in FIG. 3, a transmission electron micrograph is shown in FIG. 4.

比较例2使用玻璃珠磨机,在60g甲基丙烯酸甲酯(SP值8.7)将30gテイカ制的硅处理氧化锌(MZ-507S)搅拌3小时(用大塚电子制ELS-8000测定的氧化锌的平均粒径是0.3μm)。 Comparative Example 2 using a glass bead mill, a silicon-treated zinc oxide 30g Tayca manufactured (MZ-507S) was stirred in 60g of methyl methacrylate (SP value 8.7) for 3 hours (measured by Otsuka Electronics Ltd. ELS-8000 zinc oxide the average particle size is 0.3μm). 此后,加入2.1g过氧化月桂酰。 Thereafter, 2.1g of lauroyl peroxide. 在500g离子交换水中溶解5g月桂基硫酸钠,加入上述的氧化锌浆中,使用マイルダ进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是2.2μm)。 In 500g of ion-exchanged water was dissolved 5g sodium lauryl sulfate, was added to the zinc oxide slurry, using Hikaru the inter microspheres were dispersed (manufactured by Horiba, Ltd. The average particle diameter of the emulsion measured by LA-910 was 2.2μm). 接着,将该分散液装入2000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至70℃,在70℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行10小时聚合。 Subsequently, the dispersion was charged in a separable 2000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 70 ℃, maintained at 70 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 10 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到70g复合聚合物粒子(氧化锌的内包率30质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to obtain 70g of polymer composite particles (encapsulated by mass of zinc oxide 30%).

得到的复合聚合物粒子的扫描电子显微镜照片示于图3中,透射电子显微镜照片示于图4中。 The obtained scanning electron micrograph of the composite polymer particles are shown in FIG. 3, a transmission electron micrograph is shown in FIG. 4.

比较例3使用玻璃珠磨机,在40g甲基丙烯酸酯月桂酯(SP值8.7)、40g乙二醇二甲基丙烯酸酯、20g庚烷中将20gテイカ制的硅处理氧化锌(MZ-700:按照目录的粒径是0.02μm,未硅处理)搅拌3小时。 Comparative Example 3 mill using glass beads, at 40g methacrylate, lauryl acrylate (SP value 8.7), 40g of ethylene glycol dimethacrylate, zinc oxide, silicon-treated in the alkoxy 20g 20g heptane manufactured by Tayca (MZ-700 : directory according to particle size is 0.02μm, non-silicon-treated) for 3 hours. 此后,加入1.6g2,2′-偶氮二-2,4-二甲基戊腈。 Thereafter, 1.6g2,2'- azobis-2,4-dimethylvaleronitrile. 在500g离子交换水中溶解6.5g月桂基硫酸钠,加入上述的氧化锌浆中,使用マイルダ-进行分散(用堀场制作所制LA-910测定的乳液的平均粒径是2.0μm)。 In 500g of ion-exchanged water was dissolved 6.5g of sodium lauryl sulfate, was added to the zinc oxide slurry, using microspheres were Hikaru the inter - dispersion (produced by Horiba LA-910 prepared emulsion was measured an average particle size 2.0μm). 接着,将该分散液装入1000mL的可分离烧杯中,氮气置换后,一边以200r/min搅拌,一边升温至60℃,在60℃保持10小时,再升温至80℃,在80℃在氮气气氛下进行4小时聚合。 Subsequently, the dispersion was charged in a separable 1000mL beaker, after nitrogen substitution, while at 200r / min stirring, the temperature was raised to 60 ℃, maintained at 60 ℃ 10 hours and then heated to 80 ℃, at 80 deg.] C in a nitrogen for 4 hours under an atmosphere of polymerization. 聚合结束后,用离心分离集中固体,用水洗净,冷冻干燥后,用喷射粉碎机进行粉碎,得到70g复合聚合物粒子(氧化锌的内包率20质量%)。 After completion of the polymerization, the solid concentration by centrifugation, washed with water, freeze-dried and pulverized with a jet mill to obtain 70g of polymer composite particles (encapsulated by mass of zinc oxide, 20%).

试验例1关于在实施例1~5和比较例1~3中得到的复合聚合物粒子,用以下的方法测定SPF值。 Example 1 Test on the SPF value of 1 to 5 and the composite polymer particles of Comparative Examples 1 to 3 obtained in Examples were measured by the following method. 并且用下述方法评价对制品的配合性和使用感。 And evaluation of feeling in use and with articles by the following method. 结果示于表1中。 The results are shown in Table 1.

<SPF的测定> & Lt; Measurement of SPF & gt;

·配合组成1.聚醚改性硅(东レ·ダウコ-ニング·シリコ-ン(株)制,SH3775M):1.8质量%2.二癸酸新戊二醇酯:2.0质量%3.角鲨烷:4.0质量%4.4-甲氧基肉桂酸(2-乙基己酯):1.0质量%5.直链二甲基硅(2cs):36.0质量%6.复合聚合物粒子:作为金属氧化物5.0质量%7.甘油:4.3质量%8.水:余量·配合顺序a)均匀配合成分1~4,再加入成分5和6的分散液进行分散。 · With Composition 1. Polyether-modified silicone (manufactured by Toray · DOW U - Ni nn Corning · Silicone Co. - nn (Ltd.), SH3775M):.. 1.8 mass% 2 dicaprate neopentyl glycol: 2.0 mass% 3 dogfish alkoxy: 4.4 - 4.0% by mass methoxy cinnamate (2-ethylhexyl): 5 1.0% by mass linear dimethyl silicone (2cs):.. 36.0% by mass of the composite polymer particles 6: metal oxide 7 5.0% by mass glycerin: 4.3% by mass of water 8: * balance complex sequence a) uniformly ingredients 1 to 4, and then added to the dispersion of ingredients 5 and 6 were dispersed.

b)混合成分7和8。 b) mixing the ingredients 7 and 8.

c)在a)中慢慢添加b),使用高速混合器制成乳化物。 c) b was slowly added in a)), an emulsion made using a high speed mixer.

·试料调制准备医疗用胶带(贯通微孔外科用胶带)。 · Sample preparation modulation medical tape (through microporous surgical tape). 用注射器将80μL上述的乳化物放置在5×8cm2的胶带上,在一面用手指扩展。 80μL syringe with the above-described emulsion is placed on the tape 5 × 8cm2, extended on one side with a finger.

·SPF测定在简易型SPF测定器(labsphere制,UV TRANSMITTANCE ANALYZER)上放置上述的试料,进行测定。 · SPF measurement sample was placed on the above-described SPF Simple tester (manufactured by Labsphere, UV TRANSMITTANCE ANALYZER), was measured. 测定5次,采用平均值(四舍五入下一位数)。 Measured five times, an average value (rounded to the next digit).

<对制品的配合性和使用感的评价法> & Lt; Evaluation of feeling in use and with the article & gt;

对制品的配合性,按照下述的基准、以3等级评价和上述SPF测定用相同的配合组成下的1个月的保存稳定性,另外使用感,由1名专门小组成员,按照下述的基准、以3等级评价和上述SPF测定用相同的配合组成下的触感。 The complexes of the article, in accordance with the following criteria to evaluate level 3 SPF measurement and said storage stability for 1 month under the same composition with the addition feeling of use, the panelists 1, according to the following reference to the above-described three grades and SPF under the same measurement tactile mating components.

·配合性(1个月的保存稳定性)○:完全不发生凝集。 · With resistance (storage stability of a month) ○: completely agglutination does not occur.

△:看到稍微的凝集。 △: slight aggregation seen.

×:显著地看到凝集。 ×: significant agglomeration seen.

·使用感○:无异样感,能够使用。 Use feeling ○: no incongruity can be used.

△:稍微有粗涩感。 △: slightly Cuse sense.

×:感觉粗涩。 ×: feel Cuse.

表1 Table 1

试验例2采用常规方法制造表2所示组成的本发明和比较的乳液,按照下述方法评价SPF和使用感。 Test Example 2 by a conventional method for producing sheet of the present invention and the comparative composition shown emulsions 2, SPF and feeling evaluation by the following method. 结果示于表2中。 The results are shown in Table 2.

<SPF的测定法> & Lt; Determination of SPF & gt;

和试验例1记载的试料调制相同地进行调制并SPF测定相同地进行评价。 Test sample modulation and a same manner as described in Example modulated SPF measured in the same manner and evaluated.

<使用感的评价法> & Lt; Evaluation of feeling of use & gt;

关于本发明和比较的乳液,涂布在10名专门小组成员的手背上,进行感觉评价(涂布量:从各自的容器取出时,在手背上要形成直径2cm的圆)。 About the present invention and the comparative emulsions coated on the back of ten panelists performed sensory evaluation (Coating weight: from respective containers removed, to be formed on the back of 2cm diameter). 在涂布乳液时,好、也难说好或差、差的3等级进行评价,好作为1分,也难说好或差作为0.5分,差作为0分,按10人的合计,以10分表示满分。 When the emulsion is applied, good, good or bad is difficult to say, the difference between the evaluation level 3, as a good points, but also hard to say good or bad as 0.5 points, a difference of 0, 10 by a total of 10 points represents out.

表2 Table 2

实施例6、7和比较例4~8(评价方法)(1)紫外线防御效果使用SPF分析器(Optometrics公司),测定化妆品的SPF值,以下的基准表示。 Examples 6 and 7 and Comparative Examples 4 to 8. (Evaluation Method) (1) ultraviolet radiation protection effect using an SPF analyzer (an Optometries Corporation), SPF values ​​measured cosmetics, the following reference FIG.

[UVB防御效果评价基准]○:SPF值35以上。 [UVB protection effect Evaluation Criteria] ○: SPF value of 35 or more.

△:SPF值30以上、不到35。 △: SPF value of 30 or more and less than 35.

×:SPF不到30。 ×: SPF less than 30.

[UVA防御效果评价基准]○:T(UVA)不到18%。 [Evaluation Criteria of UVA protection effect] ○: T (UVA) less than 18%.

△:T(UVA)18%以上、不到20%。 △: T (UVA) more than 18%, less than 20%.

×:T(UVA)20以上。 ×: T (UVA) 20 or more.

在此,T(UVA)按照下式T(UVA)(%)=Σ320400Tλ×Δλ/Σ320400Δλ]]>Tλ:在波长λ中的透过率(%),Δλ:测定波长间隔定义。 Here, T (UVA) in accordance with the formula T (UVA) (%) = & Sigma; 320400T & lambda; & times; & Delta; & lambda; / & Sigma; 320400 & Delta; & lambda;]]> Tλ: transmittance at a wavelength λ of (% ), Δλ: measurement wavelength interval thereon.

(2)透明性(涂布时的白度)使用SPF分析器(Optometrics公司),测定化妆品的全透过光谱,从在450nm的波长中的透过率的值,以以下的基准表示。 (2) Transparency (white upon application) using an SPF analyzer (an Optometries Corporation), the total transmission spectra measured cosmetics, in the following reference values ​​represent the transmittance at a wavelength of 450nm in.

○:T(450nm)55%以上。 ○: T (450nm) 55% or more.

△:T(450nm)45%以上、不到55%。 △: T (450nm) 45% or more and less than 55%.

×:T(450nm)不到45%。 ×: T (450nm) less than 45%.

(3)使用感对在皮肤上涂布化妆品时的使用感,由5名专门小组成员,进行以无粗涩感、发粘感为舒适作为3分,以感觉稍微粗涩感或者发粘感作为2分,以感觉粗涩感或者发粘感作为1分的3等级评价,按照下述基准评价其平均值。 (3) using the sense of feeling in use during application of a cosmetic to the skin, the five panelists carried out in a non-rough feeling, stickiness 3 points as for comfort, a feeling of a little sticky feeling or sense-rough as 2 points, to sense or feel sticky feeling stuck into three grades as 1 minute, the average value was evaluated according to the following criteria.

<评价基准> & Lt; Evaluation Criteria & gt;

○:2.8分以上。 ○: 2.8 points or more.

△:2.5以上、不到2.8。 △: 2.5 or more and less than 2.8.

×:不到2.5。 ×: less than 2.5.

实施例6、7和比较例4~8采用下述的制法、按照表3所示的组成调制成液状紫外线防御化妆品。 Examples 6 and 7 and Comparative Examples 4 to 8 using the following production method, into a liquid UV-shielding cosmetic composition according to the modulation shown in Table 3. 对得到的化妆品,进行紫外线防御效果、透明性(涂布时的白度)和使用感的评价。 Cosmetics were evaluated for ultraviolet protection effect, transparency (white upon application) and the feeling in use will be. 评价结果同时示于表3中。 The evaluation results are shown in Table 3 simultaneously.

<液状紫外线防御化妆品的制法> & Lt; UV shielding cosmetic liquid production method & gt;

混合成分(5)~(7),向其中添加使用分散机充分分散在成分(8)中的粉体(1)~(4),再添加成分(9)和(10),通过进行均匀的混合,制成化妆品。 Mixing the components (5) to (7), to which is added a dispersing machine sufficiently dispersed in the powder component (1) (8) to (4), and then add the component (9) and (10), by uniformly mixed to prepare cosmetics.

表3 table 3

*1:FINBX-50(一次粒子的平均粒径0.02μm,堺化学(株))的表面进行硅处理的粉体。 * 1: (0.02μm, Sakai Chemical Industry (Co., Ltd.) The average primary particle size) of the surface of the silicon powder FINBX-50 for processing.

*2:特开平8-12526号公报、合成例2(平均大小0.6μm,平均厚度0.02μm)*3:按照特开2000-290156号公报中的实施例1制成的微粒子氧化锌·氧化钛硅分散液(28%)*4:硅SH3775C(东レ·ダウコ-ニング·シリコ-ン) * 2: Laid-Open Publication No. 8-12526, Synthesis Example 2 (average size of 0.6 m, an average thickness 0.02μm) * 3: according to Example No. 2000-290156 Laid-Open Patent Publication 1 is made of fine particles of zinc oxide-titanium oxide silica dispersion (28%) * 4: silicon SH3775C (Toray · Dow Corning inter - Ni Corning · silicone Co. nn - nn)

是本发明品的实施例6,UVA和UBB的紫外线防御效果、透明性和使用感都优良。 It is excellent in an embodiment of the present invention product 6, UBB and UVA ultraviolet protection effect, transparency and use feeling. 另外,在本发明品的实施例7中,是将一部分微粒子金属氧化物置换成微粒子高分散体的本发明品,UVA和UVB的紫外线防御效果、透明性和使用感也都优良。 Further, in an embodiment of the present invention product 7, which is partially replaced with the fine metal oxide particles of the present invention, high product dispersion, ultraviolet UVA and UVB protection effect, transparency and also excellent in feeling of use.

另一方面,不含微粒子金属氧化物、薄片状氧化锌和内包微粒子金属氧化物的聚合物粒子的任一种,不含薄片状氧化锌的,或者不含内包聚合物粒子的比较例4~8,UVB防御效果、UVA防御效果、透明性、使用感的任一个或者全部是劣化的。 On the other hand, it does not contain fine particles of metal oxides, and polymer particles of the flaky fine particles of zinc oxide and metal oxide encapsulated, non-flaky zinc oxide, or Comparative Example 1 containing no polymer particles encapsulated ~ 4 8, any UVB protective effect of UVA protection effect, transparency and use feeling in one or all deteriorated.

Claims (14)

  1. 1.一种复合聚合物粒子,该复合聚合物粒子含有用硅氧烷和/或氟化合物被覆的、平均粒径1μm以下的金属氧化物,是使相对全单体和交联剂的合计100质量份为25质量份以上、按照Fedors方法计算出的溶解度参数不到8.9的乙烯基单体和交联剂进行聚合而得到的。 A composite polymer particles, the composite particles containing the polymer with a silicone and / or fluorine compounds covered, average particle diameter of 1μm or less of the metal oxide, the relative whole is the total of monomers and crosslinkers 100 parts by mass or more to 25 parts by mass, as calculated by Fedors solubility parameter of less than 8.9 a method of polymerizing a vinyl monomer and a crosslinking agent obtained.
  2. 2.如权利要求1所述的复合聚合物粒子,其特征在于,在化妆品中,以化妆品总质量为基准,含有作为金属氧化物量相当于5质量%量的上述复合聚合物粒子和1质量%的4-甲氧基肉桂酸(2-乙基己酯),该化妆品的SPF是7以上。 The composite polymer particles according to claim 1, wherein, in cosmetics, based on the total mass of the cosmetic as a reference, a metal oxide containing an amount corresponding to an amount of 5 mass% of the composite polymer particles and 1% by mass 4-methoxycinnamic acid (2-ethylhexyl), the SPF is 7 or more cosmetic.
  3. 3.根据权利要求1或2所述的复合聚合物粒子,其中,溶解度参数不到8.9的乙烯基单体含具有可以氟化的碳原子数8以上的直链或者支链烷基的(甲基)丙烯酸烷基酯。 The composite polymer particles of claim 1 or claim 2, wherein the solubility parameter of less than 8.9 containing vinyl monomer may have a number of carbon atoms of 8 or more fluorinated linear or branched alkyl (meth yl) acrylate.
  4. 4.根据权利要求1或2所述的复合聚合物粒子,其中,溶解度参数不到8.9的乙烯基单体,含有在分子链的一个末端具有自由基聚合性基的二甲基聚硅氧烷化合物。 The composite polymer particles of claim 1 or claim 2, wherein the solubility parameter of less than 8.9 vinyl monomers containing dimethylpolysiloxane having a radical polymerizable group at one terminal of the molecular chain compound.
  5. 5.根据权利要求1或2所述的复合聚合物粒子,其中,溶解度参数不到8.9的乙烯基单体含具有可以氟化的碳原子数8以上的直链或者支链烷基的(甲基)丙烯酸烷基酯和在分子链的一个末端具有自由基聚合性基的二甲基聚硅氧烷化合物。 5. The composite polymer particles of claim 1 or claim 2, wherein the solubility parameter of less than 8.9 containing vinyl monomer may have a number of carbon atoms of 8 or more fluorinated linear or branched alkyl (meth yl) acrylic acid alkyl ester and a dimethylpolysiloxane compound having a radical polymerizable group at one terminal of the molecular chain.
  6. 6.根据权利要求1或2所述的复合聚合物粒子,其中,金属氧化物是选自由氧化锌、氧化钛和/或氧化铈组成的组中的至少一种以上。 The composite polymer particles of claim 1 or claim 2, wherein the metal oxide is selected from the group consisting of zinc oxide, titanium oxide and / or cerium oxide of at least one or more of the group.
  7. 7.根据权利要求1或2所述的复合聚合物粒子,其中,金属氧化物的含量是复合聚合物粒子全体的25~90质量%。 The composite polymer particles of claim 1 or claim 2, wherein the content of the metal oxide is a composite polymer particles of 25 to 90 mass% of the whole.
  8. 8.根据权利要求1所述的复合聚合物粒子,其中,相对全单体和交联剂的合计100质量份,交联剂是0.1~75质量份。 8. The composite polymer particles according to claim 1, wherein the total of 100 parts by mass relative to the whole monomer and a crosslinking agent, the crosslinking agent is 0.1 to 75 parts by mass.
  9. 9.权利要求1或2所述的复合聚合物粒子的制造方法,将用硅氧烷和/或氟化合物被覆的金属氧化物、含有溶解度参数不到8.9的乙烯基单体的单体成分和交联剂分散混合后,进行悬浮聚合。 A method for producing a composite or polymer particles according to claim 9. 12 will with a silicone and / or fluorine compound-coated metal oxide, a monomer component containing a solubility parameter of less than 8.9 vinyl monomer and after cross-linking agent dispersed and mixed, suspension polymerization.
  10. 10.含有权利要求1或2所述的复合聚合物粒子的化妆品。 10. The cosmetics containing the composite polymer particles of claim 1 or claim 2.
  11. 11.权利要求1或2所述的复合聚合物粒子的化妆品用途。 Cosmetic use of the composite polymer particles of claim 12 or claim 11.
  12. 12.含有权利要求1或2所述的复合聚合物粒子和其他化妆品成分或者化妆品载体的化妆品组合物。 12. A composite comprising polymer particles as claimed in claim 1 or claim 2 and a cosmetic composition or other cosmetic ingredients of cosmetic carrier.
  13. 13.含有以下的(A)、以下的(B)和权利要求10所述的化妆品的化妆品组合物,(A)一次粒子的平均粒径是0.001~0.1μm,具有紫外线防御能力和可见光的透过性的微粒子金属氧化物,(B)平均大小是0.1μm~1μm、平均厚度是0.01μm~0.2μm的薄片状氧化锌。 13 comprising the following (A), the cosmetic composition of the cosmetic is 10 or less (B), and wherein the average particle diameter (A) of the primary particles is 0.001 0.1μm ~, UV protection ability and having visible light permeability of the metal oxide particles through, (B) is the average size of 0.1μm ~ 1μm, the average thickness of the flaky zinc oxide is 0.01μm ~ 0.2μm.
  14. 14.根据权利要求13所述的化妆品组合物,相对上述成分(A)和包含在复合聚合物粒子中的金属氧化物,以0.05~0.4的质量比含有成分(B)的薄片状氧化锌。 14. The cosmetic composition according to claim 13, relative to the component (A) and a metal oxide contained in the composite polymer particles, 0.05 to 0.4 mass flaky zinc containing ratio of component (B) oxide.
CN 03158022 2002-08-08 2003-08-08 Composite polymer particle and method for preparing same CN1324078C (en)

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